CN114471591B - Hydrogen peroxide decomposition catalyst and preparation method and application thereof - Google Patents
Hydrogen peroxide decomposition catalyst and preparation method and application thereof Download PDFInfo
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- CN114471591B CN114471591B CN202011159146.2A CN202011159146A CN114471591B CN 114471591 B CN114471591 B CN 114471591B CN 202011159146 A CN202011159146 A CN 202011159146A CN 114471591 B CN114471591 B CN 114471591B
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- hydrogen peroxide
- metal oxide
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- decomposition catalyst
- peroxide decomposition
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 162
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 74
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 62
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- -1 VIB metal oxide Chemical class 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 34
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229920002472 Starch Polymers 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002674 ointment Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000003361 porogen Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 102100039111 FAD-linked sulfhydryl oxidase ALR Human genes 0.000 description 33
- 101000959079 Homo sapiens FAD-linked sulfhydryl oxidase ALR Proteins 0.000 description 22
- 239000004408 titanium dioxide Substances 0.000 description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 14
- 241000219782 Sesbania Species 0.000 description 12
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 238000006735 epoxidation reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- YROGWJLGNLJNOK-UHFFFAOYSA-N 1-chloro-1-methoxypropane Chemical compound CCC(Cl)OC YROGWJLGNLJNOK-UHFFFAOYSA-N 0.000 description 4
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 229910003438 thallium oxide Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/30—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a hydrogen peroxide decomposition catalyst, a preparation method and application thereof, wherein the hydrogen peroxide decomposition catalyst comprises 40-80 wt% of IVB metal oxide, 1-20 wt% of VIB metal oxide, 1-20 wt% of IB metal oxide and 18-58 wt% of IIIA metal oxide. The hydrogen peroxide decomposition catalyst has higher lateral pressure crushing strength and has better decomposition catalytic effect on hydrogen peroxide in methanol aqueous solution.
Description
Technical Field
The invention relates to a hydrogen peroxide decomposition catalyst, and a preparation method and application thereof.
Background
The epoxy chloropropane is an important basic organic chemical raw material and an intermediate, and is widely applied to various industrial products such as synthetic epoxy resin, chlorohydrin rubber, medicines, pesticides, surfactants, plasticizers and the like.
As disclosed in CN101747297A, continuous and stable synthesis of epichlorohydrin is realized for a long time under the condition that the conversion rate of hydrogen peroxide is higher than 97% and the selectivity of epichlorohydrin is higher than 95% by epoxidation reaction of 3-chloropropene and hydrogen peroxide in the presence of a titanium-silicon molecular sieve catalyst and a solvent methanol. However, the conversion of hydrogen peroxide is typically maintained between 97% and 99% during long run times such that the epoxidation reaction product contains 0.05% to 0.5% by weight hydrogen peroxide.
CN106140186a discloses a hydrogen peroxide decomposition catalyst and a method for decomposing hydrogen peroxide in an epoxidation reaction product of 3-chloropropene and hydrogen peroxide, wherein the catalyst contains 1 to 20 wt% of group ivb metal oxide, 1 to 20 wt% of group vi B metal oxide, 1 to 20 wt% of group ib metal oxide and 40 to 97 wt% of group iiia metal oxide, and the decomposition of hydrogen peroxide in the epoxidation reaction product is performed at a temperature of 0 to 50 ℃ and a pressure of 0.1 to 2.0MPa, so that the decomposition of hydrogen peroxide in the epoxidation reaction product can be reduced to less than 0.02 wt%. However, this patent does not disclose the side crushing strength of the catalyst. The research shows that the lateral pressure crushing strength of the catalyst prepared by the method disclosed in CN106140186A is lower than 70N/cm, the catalyst is easy to crush, and the strength requirement of the industrial fixed bed reactor on the catalyst filling is difficult to meet.
Disclosure of Invention
The invention aims to provide a hydrogen peroxide decomposition catalyst, a preparation method and application thereof.
The first aspect of the present invention provides a hydrogen peroxide decomposition catalyst comprising 40 to 80 wt% of a group IVB metal oxide, 1 to 20 wt% of a group VIB metal oxide, 1 to 20 wt% of a group IB metal oxide and 18 to 58 wt% of a group IIIA metal oxide.
Alternatively, the lateral pressure crushing strength of the hydrogen peroxide decomposition catalyst is 70 to 150N/cm, preferably 70 to 120N/cm.
Optionally, the hydrogen peroxide decomposition catalyst comprises 45 to 76 wt% group IVB metal oxide, 3 to 10 wt% group VIB metal oxide, 3 to 10 wt% group IB metal oxide and 18 to 49 wt% group IIIA metal oxide.
Optionally, the group IVB metal in the group IVB metal oxide includes one or more of titanium, zirconium and hafnium;
the VIB metal in the VIB metal oxide comprises one or more of chromium, molybdenum and tungsten;
the IB metal in the IB metal oxide is copper;
the group IIIA metal in the group IIIA metal oxide comprises one or more of aluminum, gallium, indium and thallium.
Optionally, the group IVB metal oxide includes one or more of titanium dioxide, zirconium oxide and hafnium oxide, preferably titanium dioxide;
the VIB group metal oxide comprises one or more of molybdenum trioxide, chromium trioxide and tungsten trioxide, and is preferably molybdenum trioxide;
the IB group metal oxide is copper oxide;
the group IIIA metal oxide comprises one or more of aluminum oxide, gallium oxide, indium oxide and thallium oxide, preferably aluminum oxide.
In a second aspect, the present invention provides a process for preparing the hydrogen peroxide decomposition catalyst provided in the first aspect of the present invention, the process comprising:
(1) Mixing a IIIA group metal source, a IVB group metal oxide, a binder and an auxiliary agent to obtain a first mixture; wherein the group IIIA metal source comprises a group IIIA metal hydroxide and/or a group IIIA metal oxide;
(2) Performing first drying and first roasting on the first mixture to obtain a composite metal oxide;
(3) Impregnating the composite metal oxide with an impregnating solution to obtain a second mixture; the impregnating solution contains IB group metal salt and VIB group metal salt;
(4) And (3) carrying out second drying and second roasting on the second mixture.
Optionally, the binder comprises an acidic aluminum sol and/or an alkaline silica sol;
the auxiliary agent comprises one or more of extrusion aid, pore-forming agent and paste;
the extrusion aid is one or more selected from starch, citric acid and sesbania powder;
the pore-forming agent is selected from one or more of polyethylene glycol, polypropylene glycol and alkylphenol ethoxylates, and is preferably alkylphenol ethoxylates;
the ointment is one or more selected from dilute nitric acid, water and ethanol, preferably dilute nitric acid and water.
Optionally, step (1) includes: kneading and extruding the group IIIA metal source, the group IVB metal oxide, the binder, the extrusion aid, the pore-forming agent and the paste-forming agent to form strips;
the weight ratio of the amounts of the IIIA group metal source, the IVB group metal oxide, the binder, the extrusion aid, the pore-forming agent and the paste forming agent is 100: (65-580): (110-260): (40-180): (5-40): (1-160).
Optionally, in step (2), the first drying condition includes: the temperature is 0-200 ℃ and the time is 1-120 h; the conditions of the first firing include: the temperature is 300-800 ℃ and the time is 1-48 h;
in step (3), the conditions of the impregnation include: the temperature is 0-100 ℃ and the time is 1-72 h;
in step (4), the second drying conditions include: the temperature is 50-200 ℃ and the time is 1-48 h; the conditions of the second firing include: the temperature is 300-800 ℃ and the time is 1-48 h.
In a third aspect, the present invention provides a use of the hydrogen peroxide decomposition catalyst according to the first aspect of the present invention for the catalytic decomposition of hydrogen peroxide in an aqueous methanol solution.
Optionally, the content of hydrogen peroxide in the aqueous methanol solution is 0.01 to 1.0 weight percent, and the mass space velocity of the feed liquid of the aqueous methanol solution is 0.01 to 20h -1 Or the dosage of the hydrogen oxide decomposition catalyst is 0.5-10% of the weight of the methanol aqueous solution;
the conditions of the catalytic decomposition include: the temperature is 0-200 ℃ and the pressure is 0.1-2.0 MPa.
Through the technical scheme, the side pressure crushing strength of the hydrogen peroxide decomposition catalyst is high, the industrial requirement can be met, and the hydrogen peroxide decomposition catalyst has a better decomposition catalytic effect on hydrogen peroxide in a methanol aqueous solution; the method is simple and feasible, and the hydrogen peroxide decomposition catalyst with higher side pressure crushing strength can be prepared.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a hydrogen peroxide decomposition catalyst comprising 40 to 80 wt% of a group IVB metal oxide, 1 to 20 wt% of a group VIB metal oxide, 1 to 20 wt% of a group IB metal oxide and 18 to 58 wt% of a group IIIA metal oxide.
The hydrogen peroxide decomposition catalyst can efficiently decompose hydrogen peroxide in a methanol aqueous solution, and has good side pressure crushing strength.
In a preferred embodiment, the hydrogen peroxide decomposition catalyst has a side crushing strength of 70 to 150N/cm, more preferably 70 to 120N/cm.
According to the present invention, the hydrogen peroxide decomposition catalyst may contain 45 to 76 wt% of a group IVB metal oxide, 3 to 10 wt% of a group VIB metal oxide, 3 to 10 wt% of a group IB metal oxide and 18 to 49 wt% of a group IIIA metal oxide.
According to the present invention, the group IVB metal in the group IVB metal oxide may include one or more of titanium, zirconium and hafnium; the group VIB metal in the group VIB metal oxide comprises one or more of chromium, molybdenum and tungsten; the IB group metal in the IB group metal oxide is copper; the group IIIA metal in the group IIIA metal oxide comprises one or more of aluminum, gallium, indium and thallium.
In a preferred embodiment, the group IVB metal oxide includes one or more of titanium dioxide, zirconium oxide and hafnium oxide, preferably titanium dioxide; the group VIB metal oxide comprises one or more of molybdenum trioxide, chromium trioxide and tungsten trioxide, preferably molybdenum trioxide; the IB group metal oxide is copper oxide; the group IIIA metal oxide includes one or more of aluminum oxide, gallium oxide, indium oxide and thallium oxide, preferably aluminum oxide.
In a second aspect, the present invention provides a method for preparing the hydrogen peroxide decomposition catalyst according to the first aspect, the method comprising:
(1) Mixing a IIIA group metal source, a IVB group metal oxide, a binder and an auxiliary agent to obtain a first mixture; wherein the group IIIA metal source comprises a group IIIA metal hydroxide and/or a group IIIA metal oxide;
(2) Performing first drying and first roasting on the first mixture to obtain a composite metal oxide;
(3) Impregnating the composite metal oxide with an impregnating solution to obtain a second mixture; the impregnating solution contains IB group metal salt and VIB group metal salt;
(4) And (3) carrying out second drying and second roasting on the second mixture.
The method has simple flow and convenient preparation, and can prepare the catalyst with good catalytic decomposition performance on hydrogen peroxide.
According to the present invention, the group IIIA metal source may be selected from one or more of aluminum hydroxide, aluminum oxide, gallium hydroxide and gallium oxide.
According to the invention, the binder may comprise an acidic aluminium sol and/or an alkaline silica sol, preferably an acidic aluminium sol, the content of aluminium oxide in the acidic aluminium sol may vary within a wide range, for example may be in the range of 1 to 25% by weight. Adjuvants are well known to those skilled in the art and may include, for example, one or more of extrusion aids, pore formers, and ointments; in one embodiment, the extrusion aid is selected from one or more of starch, citric acid and sesbania powder; the pore-forming agent is selected from one or more of polyethylene glycol, polypropylene glycol and alkylphenol ethoxylates, preferably alkylphenol ethoxylates; the ointment is selected from one or more of dilute nitric acid, water and ethanol, preferably dilute nitric acid and water.
In a preferred embodiment, step (1) comprises: kneading the IIIA metal source, IVB metal oxide, adhesive, extrusion aid, pore-forming agent and paste, and extruding to form the invented product.
According to the invention, the weight ratio of the amounts of group IIIA metal source, group IVB metal oxide, binder, extrusion aid, porogen and paste forming agent may vary within wide limits and may be, for example, 100: (65-580): (110-260): (40-180): (5-40): (1-160), preferably 100: (100-550): (130-260): (50-170): (10-35): (2-130).
According to the invention, the group IB metal salt and the group VIB metal salt contained in the impregnating solution are one or more of metal acid ammonium salt, metal nitrate and metal carboxylate, preferably metal acid ammonium salt and metal nitrate. In a specific embodiment, the impregnation fluid is an aqueous or alcoholic solution, preferably an aqueous solution, comprising a group ib metal salt and an ammonium salt of a group VIB metal acid.
According to the present invention, in step (2), the first drying conditions may include: the temperature is 0-200 ℃, preferably 10-150 ℃ and the time is 1-120 h, preferably 2-96 h; the conditions for the first firing include: the temperature is 300-800 ℃, preferably 400-700 ℃, and the time is 1-48 hours, preferably 2-36 hours. Drying and calcination are well known to those skilled in the art and may be carried out, for example, in a thermostatted oven and a muffle furnace, respectively. The firing atmosphere is not particularly limited, and may be, for example, an air atmosphere or an inert atmosphere, and the inert atmosphere may contain an inert gas, for example, nitrogen, helium, argon, or the like. In a preferred embodiment, the first mixture is dried at 10 to 20℃for 48 hours and then subjected to a first drying.
According to the present invention, in step (3), the conditions of impregnation may include: the temperature is 0 to 100 ℃, preferably 10 to 80 ℃, and the time is 1 to 72 hours, preferably 6 to 72 hours.
According to the present invention, in step (4), the second drying condition may include: the temperature is 50-200 ℃, preferably 80-150 ℃, and the time is 1-48 h, preferably 2-24 h; the conditions of the second firing may include: the temperature is 300-800 ℃, preferably 400-700 ℃, and the time is 1-48 h, preferably 3-36 h.
In a third aspect, the present invention provides a use of the hydrogen peroxide decomposition catalyst according to the first aspect of the present invention for the catalytic decomposition of hydrogen peroxide in an aqueous methanol solution.
According to the invention, the hydrogen peroxide content of the aqueous methanol solution is 0.01 to 1.0% by weight, preferably 0.02 to 0.6% by weight.
According to the invention, the aqueous methanol solution can be an extraction aqueous phase obtained by extracting and separating an epoxidation reaction product of the epoxidation reaction of 3-chloropropene and hydrogen peroxide. The aqueous methanol solution contains 1 to 5 weight percent of 3-chloropropene; preferably, the aqueous methanol solution is an aqueous 3-chloropropene-free aqueous methanol solution after removal of 3-chloropropene from the aqueous extraction phase.
According to the invention, the conditions for catalytic decomposition include: the temperature is 0 to 200 ℃, preferably 60 to 100 ℃, and the pressure is 0.1 to 2MPa, preferably 0.1 to 1MPa.
Catalytic decomposition of hydrogen peroxide according to the present invention may be carried out in a decomposition reactor well known to those skilled in the art, and may be, for example, one or more of a fixed bed reactor, a fluidized bed reactor and a stirred tank reactor.
In one embodiment, the hydrogen peroxide decomposition catalyst is dispersed in the decomposition reactor and flows along with the liquid, the hydrogen peroxide decomposition catalyst is used in an amount of 0.1-40% by weight of the aqueous methanol solution, the catalytic decomposition time is 0.01-24 h, preferably the hydrogen peroxide decomposition catalyst is used in an amount of 0.5-10% by weight of the aqueous methanol solution, and the catalytic decomposition time is 0.1-10 h.
In another specific embodiment, the hydrogen peroxide decomposition catalyst is fixed in the decomposition reactor, and the feed liquid time mass space velocity of the aqueous methanol solution is 0.01-20 h -1 Preferably 0.1 to 10 hours -1 。
The method has simple process and easy industrialization, can decompose most of residual hydrogen peroxide in the methanol aqueous solution before entering the methanol high-temperature rectification separation recovery tower, and can effectively eliminate the harm of higher hydrogen peroxide content in the methanol aqueous solution to the methanol high-temperature rectification separation process.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
In all examples and comparative examples, the side crushing strength of the catalyst was measured by using a ZQJ-II intelligent particle strength tester produced by Dain intelligent test mill, and the measured side crushing strength was an average value of 20 catalyst particles, referring to HG/T2782-1996 standard.
Example 1
139.73 g of aluminum hydroxide powder (alumina content: 71.56% by weight, manufactured by Shandong Botai Kogyo Co., ltd.), 241.97 g of titanium dioxide (chemical pure reagent), 90.00 g of starch (analytical pure reagent), 10.00 g of sesbania powder (manufactured by Henan Orchiku vegetable gum Co., ltd.), 264.26 g of alumina sol having an alumina content of 22.69% by weight (manufactured by Hunan Kogyo Co., ltd.), 20.00 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Hebei Kogyo Wang Huagong auxiliary Co., ltd.), and 3.00 g of dilute nitric acid having a nitric acid content of 2% by weight were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Wanan Kogyo Co., ltd.), then extruded into solid cylindrical bars having a diameter of 1.8mm, dried at 8-16 ℃ for 66 hours, dried at 55 ℃ C./8 hours, then placed in a box-type resistance furnace, heated from 8 ℃ C. To 120 ℃ C., and heated at a temperature-rising rate of 3.600 ℃ C./3.00% by weight, and cooled to a composite alumina having a temperature of 10.600% by weight, and then heated to obtain a composite alumina having a temperature of 99% by weight.
The weight ratio of the dosage of the aluminum hydroxide powder, the titanium dioxide, the acidic aluminum sol, the starch and sesbania powder, the OP-15 and 2 weight percent of nitric acid is 100:173.2:189.1:71.6:14.3:2.1.
150.00 g of a cylindrical bar composite metal oxide containing 60.01% by weight of titanium oxide and 39.99% by weight of aluminum oxide was impregnated with 250.00 g of an aqueous solution in which 12.42 g of ammonium molybdate tetrahydrate and 17.00 g of copper nitrate trihydrate were dissolved in a closed vessel at 35℃for 24 hours, then the impregnated material was dried at 85℃and 105℃for 12 hours, respectively, followed by calcining the dried material at 550℃for 20 hours, and after natural cooling, a cylindrical bar hydrogen peroxide decomposition catalyst containing 54.32% by weight of titanium oxide, 6.11% by weight of molybdenum trioxide, 3.38% by weight of copper oxide and 36.19% by weight of aluminum oxide was obtained, and the side crushing strength of the catalyst was 115.1N/cm.
The prepared hydrogen peroxide decomposition catalyst is used for decomposing hydrogen peroxide in a methanol aqueous solution in a fixed bed reactor, wherein the methanol aqueous solution contains 47.281 weight percent of methanol and 0.508 weight percent of hydrogen peroxide, and the decomposition reaction conditions are as follows: the feed mass hourly space velocity of the aqueous methanol solution was 3.0h -1 The decomposition temperature was 60℃and the decomposition pressure was 0.25MPa. Liquid samples of the feed and discharge were taken separately, and the mass fraction of hydrogen peroxide was determined according to the method disclosed in CN106140186a, the decomposition results of hydrogen peroxide being shown in table 1, where m HPO1 Represents the mass fraction of hydrogen peroxide before decomposition, m HPO2 Represents the mass fraction of hydrogen peroxide after decomposition, X HPO The decomposition rate of hydrogen peroxide is shown.
TABLE 1
| Continuous feed time/h | m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 24 | 0.508 | 0.000 | 100.0 |
Example 2
A hydrogen peroxide decomposition catalyst was prepared and decomposition of hydrogen peroxide in an aqueous methanol solution was performed by the method of example 1, except that the content of hydrogen peroxide in the aqueous methanol solution was 0.031 wt%, and the decomposition results of hydrogen peroxide are shown in Table 2.
TABLE 2
| Continuous feed time/h | m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 24 | 0.031 | 0.000 | 100.0 |
Example 3
A hydrogen peroxide decomposition catalyst was prepared by the method of example 1, except that 2% by weight of nitric acid was added in an amount of 9.00 g, and the weight ratio of the amounts of aluminum hydroxide powder, titanium dioxide, acidic aluminum sol, starch and sesbania powder, OP-15 and 2% by weight of nitric acid was 100:173.2:189.1:71.6:14.3:6.4 side crushing Strength of the catalyst 83.4N/cm, composition of the Hydrogen peroxide decomposition catalyst was the same as in example 1.
The prepared hydrogen peroxide decomposition catalyst is adopted to decompose hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor, wherein the methanol aqueous solution comprises 48.001 weight percent of methanol, 0.386 weight percent of chloropropanol monomethyl ether, 0.124 weight percent of 3-chloro-1, 2-propanediol, 0.104 weight percent of hydrogen peroxide and the balance of water. The catalyst is shaped into short strips with the length of 3-5 mm, and the conditions of the decomposition reaction are as follows: the stirring speed is 600r/min, the decomposition temperature is 60 ℃, the decomposition pressure is 0.1MPa, the catalyst dosage is 5.00% of the weight of the methanol aqueous solution, and the decomposition time is 30min. The decomposition results of hydrogen peroxide are shown in Table 3.
TABLE 3 Table 3
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.104 | 0.004 | 96.2 |
Example 4
176.08 g of aluminum hydroxide powder (alumina content: 71.56% by weight, manufactured by Shandong Botai Kogyo Co., ltd.), 221.75 g of titanium dioxide (chemical pure reagent), 90.00 g of starch (analytical pure reagent), 10.00 g of sesbania powder (manufactured by Henan Orchiku plant gum Co., ltd.), 237.99 g of alumina sol having an alumina content of 22.69% by weight (manufactured by Hunan Kogyo Co., ltd.), 20.00 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Hebei Kogyo Wang Huagong auxiliary Co., ltd.), and 30.00 g of dilute nitric acid having a nitric acid content of 2% by weight were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Hebei Kogyo Co., ltd.), then extruded into solid cylindrical bars having a diameter of 1.8mm, dried at a temperature of between 14 and 18 ℃ for 48 hours, dried at a temperature of 85 ℃ for 12 hours, then placed in a box-type resistance furnace, heated from 14 ℃ at a temperature of 5 ℃ to a temperature of 2 ℃ and a temperature of 5 ℃ at a temperature of 560 ℃ at a temperature of 2.00 ℃ and cooled down to a temperature of 5.00% by weight, and then heated to a composite alumina of metal oxide of 3.00% by weight was obtained.
The weight ratio of the dosage of the aluminum hydroxide powder, the titanium dioxide, the acidic aluminum sol, the starch and sesbania powder, the OP-15 and 2 weight percent of nitric acid is 100:125.9:135.2:56.8:11.4:17.0.
100.00 g of a cylindrical bar catalyst containing 55.00 wt% titanium dioxide and 45.00 wt% aluminum oxide was impregnated with 350.00 g of an aqueous solution in which 11.65 g of ammonium molybdate tetrahydrate and 33.41 g of copper nitrate trihydrate were dissolved in a closed vessel at 50℃for 20 hours, then the impregnated materials were dried at 80℃and 120℃for 10 hours, respectively, and then the dried materials were calcined at 500℃for 24 hours, and after natural cooling, a cylindrical bar hydrogen peroxide decomposition catalyst containing 45.64 wt% titanium dioxide, 7.88 wt% molybdenum trioxide, 9.13 wt% copper oxide and 37.35 wt% aluminum oxide was obtained, the side crushing strength of the catalyst was 108.3N/cm.
The prepared hydrogen peroxide decomposition catalyst is subjected to decomposition of hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor, wherein the methanol aqueous solution comprises 46.997 weight percent of methanol, 0.427 weight percent of chloropropanol monomethyl ether, 0.105 weight percent of 3-chloro-1, 2-propanediol, 0.349 weight percent of hydrogen peroxide and the balance of water. The catalyst is shaped into short strips with the length of 3-5 mm, and the conditions of the decomposition reaction are as follows: the stirring speed is 600r/min, the decomposition temperature is 75 ℃, the decomposition pressure is 0.2MPa, the catalyst dosage is 5.00% of the weight of the methanol aqueous solution, and the decomposition time is 30min. The decomposition results of hydrogen peroxide are shown in Table 4.
TABLE 4 Table 4
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.349 | 0.005 | 98.6 |
Example 5
61.49 g of aluminum hydroxide powder (alumina content: 71.56% by weight, manufactured by Shandong Botai Kogyo Co., ltd.), 322.55 g of titanium dioxide (chemical pure reagent), 90.00 g of starch (analytical pure reagent), 10.00 g of sesbania powder (manufactured by Henan Orchiku plant gum Co., ltd.), 158.66 g of aluminum sol having an alumina content of 22.69% by weight (manufactured by Hunan Kogyo Co., ltd.), 20.00 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Hebei Kogyo Wang Huagong auxiliary Co., ltd.), and 78.00 g of dilute nitric acid having a nitric acid content of 2% by weight were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Wanan Kogyo Co., ltd.), then extruded into solid cylindrical bars having a diameter of 1.8mm, dried at 10 to 18 ℃ C. For 48 hours, dried at 50 ℃ C./C., then dried at 24 hours, and then heated from 10 ℃ C. To 120 ℃ C., and 5.00 g at a temperature-5 ℃ C./C., and cooled at a temperature-20.00% by weight, and then heated to obtain a composite alumina having a temperature of 20.00% by weight.
The weight ratio of the dosage of the aluminum hydroxide powder, the titanium dioxide, the acidic aluminum sol, the starch and sesbania powder, the OP-15 and 2 weight percent of nitric acid is 100:524.6:258.0:162.6:32.5:126.8.
100.00 g of a cylindrical bar catalyst containing 80.00 wt% titanium dioxide and 20.00 wt% aluminum oxide was impregnated with 180.00 g of an aqueous solution in which 6.13 g of ammonium molybdate tetrahydrate and 15.19 g of copper nitrate trihydrate were dissolved in a closed vessel at 50℃for 24 hours, then the impregnated materials were dried at 85℃and 125℃for 12 hours, respectively, and then the dried materials were calcined at 550℃for 24 hours, and naturally cooled to obtain a cylindrical bar hydrogen peroxide decomposition catalyst containing 72.73 wt% titanium dioxide, 4.54 wt% molybdenum trioxide, 4.55 wt% copper oxide and 18.18 wt% aluminum oxide, the side crushing strength of the catalyst being 96.6N/cm.
The prepared hydrogen peroxide decomposition catalyst is subjected to decomposition of hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor, wherein the methanol aqueous solution comprises 47.553 weight percent of methanol, 0.414 weight percent of chloropropanol monomethyl ether, 0.078 weight percent of 3-chloro-1, 2-propanediol, 0.525 weight percent of hydrogen peroxide and the balance of water. The catalyst is shaped into short strips with the length of 3-5 mm, and the conditions of the decomposition reaction are as follows: the stirring speed is 600r/min, the decomposition temperature is 90 ℃, the decomposition pressure is 0.3MPa, the catalyst dosage is 5.00% of the weight of the methanol aqueous solution, and the decomposition time is 30min. The decomposition results of hydrogen peroxide are shown in Table 5.
TABLE 5
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.525 | 0.005 | 99.0 |
Example 6
A hydrogen peroxide decomposition catalyst was prepared and decomposition of hydrogen peroxide was performed in an aqueous methanol solution by the method of example 3, except that the aqueous methanol solution contained 2.708% by weight of 3-chloropropene, 47.115% by weight of methanol, 0.397% by weight of chloropropanol monomethyl ether, 0.106% by weight of 3-chloro-1, 2-propanediol, 0.046% by weight of hydrogen peroxide and the balance of water, the decomposition temperature of hydrogen peroxide was 60℃and the decomposition results of hydrogen peroxide are shown in Table 6.
TABLE 6
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.046 | 0.010 | 78.3 |
Example 7
A hydrogen peroxide decomposition catalyst was prepared and decomposition of hydrogen peroxide in an aqueous methanol solution was performed by the method of example 3, except that the decomposition temperature of hydrogen peroxide was 35℃and the decomposition results of hydrogen peroxide were shown in Table 7.
TABLE 7
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.104 | 0.017 | 83.7 |
Comparative example 1
A hydrogen peroxide decomposition catalyst was prepared according to the method of example 1 disclosed in CN106140186A, to give a cylindrical bar composite metal oxide catalyst comprising 13.39% by weight of titanium oxide, 6.11% by weight of molybdenum trioxide, 3.38% by weight of copper oxide and 77.12% by weight of aluminum oxide, the side crushing strength of the catalyst being 48.7N/cm, and the weight ratio of the amounts of aluminum hydroxide powder, titanium oxide, acidic aluminum sol, starch and sesbania powder, OP-15 and 2% by weight of nitric acid being 100:17.8:140.8:22.5:7.5:16.5.
The prepared hydrogen peroxide decomposition catalyst was subjected to decomposition of hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor under the same conditions as in example 3, and the decomposition results of hydrogen peroxide are shown in Table 8.
TABLE 8
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.104 | 0.006 | 94.2 |
Comparative example 2
A hydrogen peroxide decomposition catalyst was prepared according to the method of example 2 disclosed in CN106140186A, to give a cylindrical bar composite metal oxide catalyst comprising 12.62% by weight of titanium oxide, 11.52% by weight of molybdenum trioxide, 3.18% by weight of copper oxide and 72.68% by weight of aluminum oxide, the side crushing strength of the catalyst being 37.6N/cm, and the weight ratio of the amounts of aluminum hydroxide powder, titanium oxide, acidic aluminum sol, starch and sesbania powder, OP-15 and 2% by weight of nitric acid being 100:17.8:140.8:22.5:7.5:16.5.
The prepared hydrogen peroxide decomposition catalyst was subjected to decomposition of hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor under the same conditions as in example 3, and the decomposition results of hydrogen peroxide are shown in Table 9.
TABLE 9
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.104 | 0.006 | 94.2 |
Comparative example 3
A hydrogen peroxide decomposition catalyst was prepared according to the method of example 3 disclosed in CN106140186A, to give a cylindrical bar composite metal oxide catalyst comprising 13.35% by weight of titanium oxide, 3.05% by weight of molybdenum trioxide, 6.74% by weight of copper oxide and 76.86% by weight of aluminum oxide, the side crushing strength of the catalyst being 45.9N/cm, and the weight ratio of the amounts of aluminum hydroxide powder, titanium oxide, acidic aluminum sol, starch and sesbania powder, OP-15 and 2% by weight of nitric acid being 100:17.8:140.8:22.5:7.5:16.5.
The prepared hydrogen peroxide decomposition catalyst was subjected to decomposition of hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor under the same conditions as in example 3, and the decomposition results of hydrogen peroxide are shown in Table 10.
Table 10
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.104 | 0.003 | 97.1 |
From the above results of the decomposition of hydrogen peroxide, it is found that the mass fraction of hydrogen peroxide in the aqueous methanol solution can be reduced from 0.031 to 0.525% to 0.01% or less under preferable conditions by the method of the present invention. By contrast, the method of the comparative example can also make the mass fraction of hydrogen peroxide in the aqueous methanol solution lower than 0.01%, but the side pressure crushing strength of the catalyst is obviously lower than 70N/cm, so that the catalyst is easy to crush, and the strength requirement of the industrial fixed bed reactor on the catalyst filling is difficult to meet.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (8)
1. A hydrogen peroxide decomposition catalyst, which is applied to the catalytic decomposition of hydrogen peroxide in a methanol aqueous solution; the hydrogen peroxide decomposition catalyst comprises 45-76 wt% of IVB metal oxide, 3-10 wt% of VIB metal oxide, 3-10 wt% of IB metal oxide and 18-49 wt% of IIIA metal oxide; the IVB metal in the IVB metal oxide is titanium; the VIB metal in the VIB metal oxide is molybdenum; the IB metal in the IB metal oxide is copper; the group IIIA metal in the group IIIA metal oxide is aluminum;
the lateral pressure crushing strength of the hydrogen peroxide decomposition catalyst is 70-150N/cm; the aqueous methanol solution is an aqueous methanol solution which does not contain 3-chloropropene after 3-chloropropene is removed from an extraction aqueous phase;
the conditions of the catalytic decomposition include: the temperature is 60-100 ℃ and the pressure is 0.1-1 MPa;
the hydrogen peroxide decomposition catalyst is prepared by the following method:
(1) Kneading and extruding a IIIA group metal source, a IVB group metal oxide, a binder, an extrusion aid, a pore-forming agent and a paste forming agent to obtain a first mixture; wherein the group IIIA metal source comprises a group IIIA metal hydroxide and/or a group IIIA metal oxide;
(2) Performing first drying and first roasting on the first mixture to obtain a composite metal oxide;
(3) Impregnating the composite metal oxide with an impregnating solution to obtain a second mixture; the impregnating solution contains IB group metal salt and VIB group metal salt;
(4) And (3) carrying out second drying and second roasting on the second mixture.
2. The hydrogen peroxide decomposition catalyst according to claim 1, wherein the hydrogen peroxide decomposition catalyst has a side crushing strength of 70 to 120N/cm.
3. The hydrogen peroxide decomposition catalyst according to any one of claims 1 to 2, wherein the group ivb metal oxide is titania;
the VIB group metal oxide is molybdenum trioxide;
the IB group metal oxide is copper oxide;
the group IIIA metal oxide is alumina.
4. The hydrogen peroxide decomposition catalyst of claim 1, wherein the binder comprises an acidic aluminum sol and/or an alkaline silica sol;
the extrusion aid is one or more selected from starch, citric acid and sesbania powder;
the pore-forming agent is one or more selected from polyethylene glycol, polypropylene glycol and alkylphenol ethoxylates;
the ointment is one or more selected from dilute nitric acid, water and ethanol.
5. The hydrogen peroxide decomposition catalyst of claim 4, wherein the porogen is alkylphenol ethoxylate; the ointment is diluted nitric acid and water.
6. The hydrogen peroxide decomposition catalyst of claim 1, wherein the group iiia metal source, the group ivb metal oxide, the binder, the extrusion aid, the porogen, and the paste forming amount are present in a weight ratio of 100: (65-580): (110-260): (40-180): (5-40): (1-160).
7. The hydrogen peroxide decomposition catalyst of claim 1, wherein in step (2), the first drying conditions comprise: the temperature is 0-200 ℃ and the time is 1-120 h; the conditions of the first firing include: the temperature is 300-800 ℃ and the time is 1-48 h;
in step (3), the conditions of the impregnation include: the temperature is 0-100 ℃ and the time is 1-72 h;
in step (4), the second drying conditions include: the temperature is 50-200 ℃ and the time is 1-48 h; the conditions of the second firing include: the temperature is 300-800 ℃ and the time is 1-48 h.
8. The hydrogen peroxide decomposition catalyst according to claim 1, wherein the hydrogen peroxide content in the aqueous methanol solution is 0.01 to 1.0 wt%, and the feed liquid hourly space velocity of the aqueous methanol solution is 0.01 to 20h -1 Alternatively, the hydrogen oxide decomposition catalyst is used in an amount of 0.5 to 10% by weight of the aqueous methanol solution.
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| WO2007131438A1 (en) * | 2006-05-08 | 2007-11-22 | Zhaoqing Shunxin Coal Chemical Industry S.T. Co., Ltd. | Main hydrogenation catalyst for coal liquefaction hydrogen supplying solvent and method of preparation thereof |
| WO2011075279A1 (en) * | 2009-12-16 | 2011-06-23 | Lyondell Chemical Technology, L.P. | Titania-alumina supported palladium catalyst |
| CN102259023A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve catalyst and preparation method and use thereof |
| CN106140186A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method of decomposition of hydrogen peroxide in decomposition catalyst and epoxidation reaction product thereof |
| CN110935432A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide composite oxide and preparation method thereof |
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2020
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007131438A1 (en) * | 2006-05-08 | 2007-11-22 | Zhaoqing Shunxin Coal Chemical Industry S.T. Co., Ltd. | Main hydrogenation catalyst for coal liquefaction hydrogen supplying solvent and method of preparation thereof |
| WO2011075279A1 (en) * | 2009-12-16 | 2011-06-23 | Lyondell Chemical Technology, L.P. | Titania-alumina supported palladium catalyst |
| CN102259023A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve catalyst and preparation method and use thereof |
| CN106140186A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method of decomposition of hydrogen peroxide in decomposition catalyst and epoxidation reaction product thereof |
| CN110935432A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide composite oxide and preparation method thereof |
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